Kinetics of the high-temperature combustion reactions of dibutylether using composite computational methods

Handle URI:
http://hdl.handle.net/10754/565988
Title:
Kinetics of the high-temperature combustion reactions of dibutylether using composite computational methods
Authors:
Rachidi, Mariam El ( 0000-0001-7392-6777 ) ; Davis, Alexander C.; Sarathy, Mani ( 0000-0002-3975-6206 )
Abstract:
This paper investigates the high-temperature combustion kinetics of n-dibutyl ether (n-DBE), including unimolecular decomposition, H-abstraction by H, H-migration, and C{single bond}C/C{single bond}O β-scission reactions of the DBE radicals. The energetics of H-abstraction by OH radicals is also studied. All rates are determined computationally using the CBS-QB3 and G4 composite methods in conjunction with conventional transition state theory. The B3LYP/6-311++G(2df,2pd) method is used to optimize the geometries and calculate the frequencies of all reactive species and transition states for use in ChemRate. Some of the rates calculated in this study vary markedly from those obtained for similar reactions of alcohols or alkanes, particularly those pertaining to unimolecular decomposition and β-scission at the α-β C{single bond}C bond. These variations show that analogies to alkanes and alcohols are, in some cases, inappropriate means of estimating the reaction rates of ethers. This emphasizes the need to establish valid rates through computation or experimentation. Such studies are especially important given that ethers exhibit promising biofuel and fuel additive characteristics. © 2014.
KAUST Department:
Clean Combustion Research Center
Publisher:
Elsevier BV
Journal:
Proceedings of the Combustion Institute
Issue Date:
2015
DOI:
10.1016/j.proci.2014.05.109
Type:
Article
ISSN:
15407489
Appears in Collections:
Articles; Clean Combustion Research Center

Full metadata record

DC FieldValue Language
dc.contributor.authorRachidi, Mariam Elen
dc.contributor.authorDavis, Alexander C.en
dc.contributor.authorSarathy, Manien
dc.date.accessioned2015-08-12T08:58:19Zen
dc.date.available2015-08-12T08:58:19Zen
dc.date.issued2015en
dc.identifier.issn15407489en
dc.identifier.doi10.1016/j.proci.2014.05.109en
dc.identifier.urihttp://hdl.handle.net/10754/565988en
dc.description.abstractThis paper investigates the high-temperature combustion kinetics of n-dibutyl ether (n-DBE), including unimolecular decomposition, H-abstraction by H, H-migration, and C{single bond}C/C{single bond}O β-scission reactions of the DBE radicals. The energetics of H-abstraction by OH radicals is also studied. All rates are determined computationally using the CBS-QB3 and G4 composite methods in conjunction with conventional transition state theory. The B3LYP/6-311++G(2df,2pd) method is used to optimize the geometries and calculate the frequencies of all reactive species and transition states for use in ChemRate. Some of the rates calculated in this study vary markedly from those obtained for similar reactions of alcohols or alkanes, particularly those pertaining to unimolecular decomposition and β-scission at the α-β C{single bond}C bond. These variations show that analogies to alkanes and alcohols are, in some cases, inappropriate means of estimating the reaction rates of ethers. This emphasizes the need to establish valid rates through computation or experimentation. Such studies are especially important given that ethers exhibit promising biofuel and fuel additive characteristics. © 2014.en
dc.publisherElsevier BVen
dc.subjectCombustionen
dc.subjectComputational kineticsen
dc.subjectDibutyl etheren
dc.subjectTransition state theoryen
dc.titleKinetics of the high-temperature combustion reactions of dibutylether using composite computational methodsen
dc.typeArticleen
dc.contributor.departmentClean Combustion Research Centeren
dc.identifier.journalProceedings of the Combustion Instituteen
dc.contributor.institutionNational Institute of Standards and Technology, Gaithersburg, MD, USAen
kaust.authorSarathy, Manien
kaust.authorRachidi, Mariam Elen
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